Method of forming metal complexcontaining concentrates



March 26, 1963 H. D. KLUGE ETAL 3,083,161

METHOD OF FORMING METAL COMPLEX-CONTAINING CONCENTRATES Filed Dec. 3l, 1958 oww United States Patent O 3,033,161 METHOD F FORMING METAL COMPLEX- CONTAlNING CONCENTRATES Herman D. Kluge, Morris A. Wiley, and Kenneth L.

Kreuz, Fishkill, N.Y., assignors to Texaco Ille., a corporation of Delaware Filed Dec. 31, 1958, Ser. No. 784,109 17 Claims. (Cl. 252-32.7)

This invention relates to a method of forming metal complexes in a base oil to obtain concentrates useful as additives for lubricating and fuel preparations. This application is a continuation-impart of application Serial No. 645,667, tiled March 13, 1957, now abandoned.

ln co-pending, co-assigned application Serial No. 747,089, led July 7, 1958, by Morris A. Wiley and Herman I. Kluge, an inorganic metal base, a metal carboxylate and a dispersant are heated in a lubricating oil at from 400 to 850 F. and preferably from 600 to 700 F. for a given length of time under non-oxidizing conditions to obtain metal complex-containing concentrates.

In co-pending, co-assigned application Serial No. 746,645, filed luly 7, 1953, by Morris A. Wiley, an inorganic metal `base, a metal carboxylate and a dispersant are heated in a lubricating oil at from 325 to 550 F. and preferably from 400 to 500 F. while blowing with an oxygen containing gas for a given period of ktime to obtain a metal complex-containing concentrate.

The processes of the co-pcnding applications and that of the present invention incorporate substantial amounts of dispersed metal compounds in a base oil at relatively low cost per unit of added metal and permit excellent control of the amounts of metal nally present in the product.

ln accordance with the present invention, the method of `forming metal complex-containing concentrates cornprises heating a basic-reacting inorganic metal compound in a lubricating oil in the presence of a dispersant at a temperature of at least 350 F. and preferably from 400 to 550 F. while blowing with an oxygen-containing gas during said heating for a time sutiicient to produce a metal complex-containing concentrate having a high amount of metal dispersed therein.

The basic reacting inorganic metal compounds useful for this invention include those capable of reacting with lubricating oil oxidation products, such as the oxides, hydroxides and carbonates of alkali metals and alkaline earth metals. Of the aforementioned basic compounds, the barium compounds are preferred. The amount of basic metal compound used generally must be at least sutlicient to neutralize or saponify any acidic material formed under the reaction conditions. Advantageously in order to obtain better yields amounts within the range of from 20 to 400 percent in excess of the stoichiometric quantity theoretically required for neutralization and saponication of the formed acidic material are employed. Preferably the basic metal compound should be present in the amount of from 50 to 200 (wt.) percent in excess of the stoichiometric quantity required. As a practical matter experience has indicated that the basic metal compound should be present in amounts ranging from l to 35 (wt.) percent and preferably from to 20 (wt.) percent based on the total reaction mixture.

The dispersants used in the method of this invention are metal salts of organic acids having high solubility in lubricating oils and which must be heat stable at temperatures of at least 350 F. and preferably as high as 800 F. Examples of the dispersants include normal, basic and superbased oil soluble petroleum (mahogany) sulfonates. Synthetic sulfonates such as alkyl aryl sulfonates derived from alkylated benzene or naphthalene 3,083,161 Patented Mar. 26, 1963 may be used. Other useful dispersants include metal alkyl phenolates or sulfurized alkyl phenolates, the alkyl groups in each case having at least 8 carb-on atoms, and advantageously from 8 to 60 carbon atoms; salts of alkyl phenol-formaldehyde condensation products; salts of hexamethylene tetramine-alkyl phenol condensation products; naphthenates and naphthenic acids; and the metal salts of olefin polymer-phosphorus sulde reaction products wherein the olefin polymer has a molecular weight ranging from 400 to 10,000.

Preferred dispersants for this invention include oilsoluble metal petroleum sulfonates made from a sulfonic acid having a molecular weight of about 350 to 450, and the metal salts of a polyisobutylene-P2S5 reaction product wherein the polyisobutylene has an average molecular weight of from 500-1500.

Usually, the dispersant material is initially incorporated in the reaction mass in a nished state, however, the disersant precursor acid material, for example the sulfonic acid, is at times added initially to the reaction mass and the detergent formed in situ by reaction with the basicreacting inorganic metal compound under the prescribed reaction conditions.

The amount of the dispersant used is dependent on the amount of metal compounds to be dispersed in the concentrate. Generally, the amount of dispersant used is from 1.0 to 40.0 (mol) percent and preferably 4.0 to 20.0 (mol) percent of the stoichiometric quantity of the metal employed in this process.

The method of this invention is carried out in either one or two temperature stages. In the preferred practice of the present invention, heating is carried out in two temperature stages. The first temperature stage ranges from 250 to 400 F. and preferably no lower than 325 F. which is the temperature range wherein acidic products of oxidation of the lubricating oil are formed and readily unite with the metal base present to produce metal carboxylates. The tirst stage heating is carried out for a time sufcient to produce the desired carboxylate material. This time period broadly ranges from about 1 hour to 15 hours and preferably from about 4 to 8 hours depending on the temperature used, the susceptibility of the particular hydrocarbon stock to oxidation and the rate of air blowing employed.

The second temperature stage is carried out at least 50 F. higher than said first heating stage and at a temperature of at least 350 F. to just below the decomposition temperature of the oil which is generally from 700 to 850 F. Preferably, the second stage is carried out between 400 and 550 F. to obtain decomposition of the metal carboxylate material formed in the first temperature stage. The time period for the second stage of heating ranges from 10 minutes to 5 hours depending on the second stage `temperature and the degree of oxygen blowing. Preferably the time range for this stage is from 1/5. hour to 2 hours.

Heating from ambient temperature to the first `temperature stage is usually carried out in a time period ranging from about 20 minutes to 3 hours and preferably from 1 to 2 hours. The time period for raising the temperature from the first stage to the second stage is usually from 15 to 90 minutes and preferably from 30 minutes to an hour.

The blown oxygen-containing gas useful for this invention is conventionally air but pure oxygen, ozone, or mixture of oxygen and other gas wherein the oxygen is present in amounts sufficient to cause oxidation under the temperature and time limitations outlined for the process of this invention are useful. The rate of air blowing is generally 0.1 to 10.0 liters per minute per liter of the mixture in the reacting vessel. Preferably the rate of air blowing is from 0.2 to 3 liters per minute per liter of reaction mixture. Although more costly, oxygen blowing at a rate of 0.05 to 2.0 liters per minute, preferably from about 0.1 to 0.5 liter per minute per liter of charge, may be employed instead of air blowing.

Water is desirably employed in the reaction to hydrate a metal oxide `base or to promote saponitication and reactiveness of the metal base compounds. Generally, about 1.0 to 30 (wt.) percent of water based on weight of the charge materials and preferably 5.0 to percent of water is added to the reaction mixture.

The base oils which are used in the process of this invention are hydrocarbon oils both of the natural and synthetic type. Naphthene, paraffin and residual type mineral lubrciating oils, and mixtures thereof are normally employed. These oils include those which have been subjected to all types of refining techniques including solvent refining, dewaxing and hydroretining. Synthetic base fluids such as polybutenes having molecular weight ranging from 200-800 are also included.

Examples of typical mineral oils of lubricating grade which have been treated by our process are the following three prepared by distillation from a parailin base crude oil followed by furfural refining, light acid treating, clay contacting, and solvent dewaxing. The oil designations here used will be carried into the examples.

O11 A i B Viscosity, SUS at 2100 Il. '73, 2 43.5 (i5. 4 Flash Point., COC, o F -115 Ali Gravity, OA PI .20. 3 31.7 20.1 Sulfur content, wt. percent. 0. 30 0.11 0. 29 Ash, wt.. percent O Util (1.001 Viscosity Iullu.; 00

In carrying out the process of the invention, it has been found that excellent results are obtained by maintaining the temperature between 350 and 450 F., with the iirst stage near the lower value and the second stage near the higher. The higher the temperature the more rapid is the reaction, and the greater is the amount of barium or other metal incorporated in the oil. For example, at a temperature of 400 F. six hours of air blowing were required to incorporate about 2.5% of barium in mineral oil A, whereas at 450 F. only one hour was required for the same results, in one stage operation. Excellent results have been obtained by blowing with air for more than 2 hours at 350 F. followed by heating to 450 F. with continued air blowing, and then, if desired, air blowing for about 1 hour at 450 F.

It should also be noted that the amount of barium or other metal incorporated by our process increases with the time of oxidation as well as with the temperature. For example, in one stage operation, at 450 F. two hours of oxidation resulted in a little less than 4% of barium being incorporated, whereas more than 6% of barium was incorporated in four hours.

Furthermore, holding the composition at the upper temperature stage for a. period of time for example from minutes to one hour after air blowing has ceased causes an additional `increment of metal to be incorporated in the oil and produces a concentrate of reduced viscosity. During such holding period, agitation and air exclusion are obtained by blowing nitrogen, argon or other inert gas through the oil. Air exclusion also may be accomplished by vacuum operation.

At times, in order to convert any remaining metal oxide or hydroxide still present in the complex, or dispersed in colloidal form, to a neutral salt, the product is carbon dioxide blown at about 15G-450 F., conveniently at 250 to 350 F. for about ve minutes to four hours. Other acidic gases such as hydrogen sulde or sulfur dioxide may be employed to obtain a neutral product.

When the metal compounds have `been dispersed in mineral oil by our novel process and excess solids have been ltered out, the resulting oil concentrate composition is clear, filterable, and stable. The metal is then present primarily as a dispersion of its carbonate in the oil, rather than solely as carboxylate salts which result both from the addition of the metal hydroxide to an oil subsequent to air blowing, and from air blowing at too low la temperature. To date the best results have been obtained with barium: barium concentrates range between 1 and 25% by weight of barium, 50% or more of which is generally present `as the carbonate. With other metals, less is incorporated, such as 0.5-2% calcium, 0.1-1% magnesium, 0.5-2% sodium, and about l-6% potassium.

The method of this invention produces metal complexcontaining concentrates having dispersed therein from 0.1-15 weight percent metal carbonate, from 1-40 weight percent dispersant and from 0.5-30 weight percent metal carboxylate; the metal being present in the oil in an amount of at least 0.25 weight percent and not exceeding 25 percent.

The metal complex is an excellent detergent additive for hydrocarbon compositions notably lubricants. It is generally incorporated in lubricants in amounts wherein the metal compound content is from 0.01 to 5 percent by weight of the total lubricant composition.

The metal complex additives prepared in accordance with this invention are ciiective detergent additives for crankcase lubricants employed in internal combustion engines. They are especially useful as alkaline additives for cylinder lubricants for diesel engines operating on low quality distillate or residual fuels. Such lfuels often contain high amounts of sulfur, vanadium and other materials normally corrosive to metal engine parts, particularly rings and liners. These metal complexes, particularly the alkaline earth metal derivatives, are effective in controlling deposits and in preventing the usually high rates of corrosive Wear normally associated with the use of low quality fuels in diesel engines.

Examples of thc process of this invention are given as follows:

Erample l 1836 grams of barium oxide powder were mixed with 5400 grams of oil B, and 216 ml. water were added on top. While stirring, air was then blown through the mixture at a rate of 16 liters per minute (L/min.) (equivalent to about 2.4 l./l./rnin.) until the temperature of the oil reached 350 F. 600 grams of basic barium petroleum (mahogany) sulfonate (11% Ba; molecular weight of sulfonic acid radical about 450) then were added and oxidation was continued three hours at 350. The mixture was then heated gradually over l hour to 450 F. and heated 1 hour at 450 F. while air blowing was continued. After filtering and cooling the resulting concentrate product was found to have the following characteristics:

Viscosity-SSU at 100 F CO2, percent (wt.) 2.0 Ba, percent (wt.) 12.5 Basic barium by pcrchloric acid titration in glacial acetic acid using methyl violet indicator, percent (wt.) 11.9

12.5-]1.9=0.6% barium indicated to be present as normal barium sulfonate.

2.0 2.0 BZL=E X 131 .426.20 barium equivalent to the CO2 present.

X: se et.

solution was combined with the first, the barium metal having been removed from the ether solution and this solution being substantially free of mineral acid. The ether was evaporated under vacuum at ambient temperatures and the resulting organic layer dried over anhydrous sodium sulfate to yield an oil solution of organic acids and oxidized materials obtained from the barium additive concentrate. Tests on this product were:

Carbonyl No 6 Neutralization No 17.1 Saponification No 21.7 Ester No. (21.7*17.1=4.6) 4.6 Hydroxyl No 6 These tests indicated a relatively low concentration of ether soluble oxidized materials to have been present in the original barium additive concentrate. Stoichiometric reaction of barium with the acids, esters and alcohols indicated to be present in this oily material by these tests with formation of both barium soaps and barium alcoholates or other barium salts could account for only 4 grams of barium per 100 grams of extracted oil.

The conclusion was that this barium additive concentrate was substantially a dispersion of inorganic barium bases (predominantly barium carbonate) containing some barium salts of oxidized lubricating oil and a minor proportion of dissolved barium petroleum sulfonate. Infrared analysis is consistent with this interpretation.

Example Il 2,700 grams of oil A, 459 grams of barium oxide (1 mol/kg. oil) and 54 ml. of water were mixed and blown with 10 1./min. of air while heating to 350 F. Then 300 grams of basic barium petroleum sulfonate (11% Ba) were added as a liquid and the oxidation was continued three hours at 350, at which time a ltered sample contained 0.68% Ba. The temperature was then gradually raised over one hour to 450, at which time a filtered sample contained 3.53% Ba. After continuing oxidation for one hour at 450, the ltered product was fluid, light in color, oil soluble, and analyzed 8.7% Ba by weight.

Under similar conditions, but using 2 mois of barium oxide per kg. of oil, the product contained 13.7% of barium.

The following two examples demonstrate the effect of higher temperatures in the second stage of the process.

Example Ill 2700 grams of oil B and 1180 grams of barium carbonate were heated to 350 F. with air blowing at 10 1./rnin., and 300 grams of basic barium petroleum Sulfonate (11% Ba) were added. Oxidation then continued for ten hours at 350 F. After ltering, the product contained 1.29% Ba by weight.

Example IV 2700 grams of oil A, 300 grams of sulfurized barium alkylphenolate, 459 grams of barium oxide, and 56 rnl. of water were air blown at 12 L/rnin. for three hours at 350 F. Then the mixture was heated over 11/3 hours to 450 and heated one hour at 450. The product after three hours at 350 F. contained 0.46% Ba, but after one hour at 450, 5.2% of Ba was present.

Example V 918 grams of barium oxide were mixed with 5400 grams of oil B and S ml. water and, while stirring, air was blown through the mixture at a rate of 18.0 1./min. while heating to 350 F. Then 600 g. of basic barium petroleum sulfonate (11% Ba) was added and the oxidation was continued three hours at 350 F. The temperature was then gradually raised over one hour to 450 F. and oxidation continued for one hour at 450 F. Analyses on the filtered product and samples taken at intervals during the oxidation were:

l Eilrpressed as hydroxy] groups equivalent to milligrams of KOH/g. o!

sami? e.

2 .xpressed as carbonyl groups equivalent to milligram o1' KOU/g. oi sample.

Example Vl The effect of holding at the upper temperature after discontinuing air blowing is shown by the following data:

1836 grams of barium oxide were mixed with 5400 grams of oil B and 216 ml. of water. The reaction mixture was heated to 350 F. while stirring and blowing with air ata rate of 16 1./ min. 600 grams of basic barium petroleum sulfonate (11% Ba) was then added and oxidation was continued for three hours at 350 F. The ternrature was then gradually raised to 450 F. over a period of one hour and oxidation continued at 450 F. for one hour. A iiltered sample taken at this time contained 12.4% barium by analysis. The reaction mixture was then held at 450 F. for two hours longer while agitating the mixture by stirring and blowing with nitrogen gas. The filtered product contained 13.9% barium by analysis.

The following examples demonstrate the use of different metals in the process of the invention:

Example VII 2700 grams of oil B, 336 grams of calcium oxide, and 108 ml. of water were blown with air while heating to 350 P. Then 300 grams of basic calcium petroleum sultonate (2.9% Ca) were added and blowing continued for six hours at 350 F. The filtered product analyzed 0.9% Ca by weight.

Example VIII Under conditions similar to Example VII, but using basic barium petroleum sulfonate instead of the calcium salt, the filtered product contained 0.68% of Ca and 1.2% of Ba by weight.

Example IX 2700 g. of oil B, 444 g. of slaked lime, and 300 g. basic barium' sulionate were oxidized for 14 hours at 375 F. at an air rate of 10.0 liters per minute and the resultant product filtered. The filtered product was found to contain 1.21% calcium by weight.

Example X The materials described in Example IX in the same amounts were oxidized for 24 hours at 350 F. with 10.0 liters per minute of air and iiltered. The amount of calcium found was 1.58 percent by weight.

Example XI 168 grams of calcium oxide and 54 grams of water were mixed with 2700 grams of oil A together with 300 grams of basic calcium petroleum sulfonate (as a dispersion agent). After blowing with air at l0 1./min. for three hours at 350 F. a filtered sample contained 0.57% of calcium. The temperature was then raised over one hour to 450 F. with continued blowing for one hour at 450 F., at which time the filtered product contained 0.84% calcium.

Example X l I 2700 grams of oil B, 300 grams of basic barium petroleum sulfonate, and 444 grams of calcium hydroxide were blown with air at 10 l./min. for l0 hours at 400 F. After filtering, the product analyzed 1% of metal expressed as Ca by weight.

Example XIII 121 grams of magnesium oxide, 300 grams of basic magnesium petroleum sulfonate (2.0% Mg), and 54 ml. of water, and 2700 grams of oil A were blown with air at 10 1,/min. for 3 hours at 350 F. Then the temperature was raised over one hour to 450 F. with continued blowing which continued for one hour at 450 F. Upon filtering, the product filtrate was found to contain 0.38% of magnesium.

Example XIV 120 grams of sodium hydroxide (pellets) were mixed with 300 grams of a soluble sodium petroleum sulfonate concentrate (3% sodium; mol. wt. 450) and 2700 grams of oil A. The reaction mixture was heated to 350 F., while stirring and blowing with air at the rate of l l./min. and oxidation was continued while heating at 350 F. for three hours. The temperature was then raised slowly to 450 F. over one hour and oxidation continued for one hour at 450 F. The filtered product was clear and fluid and contained 1.6% sodium and 0.85% carbon dioxide by analysis and had an alkaline neutralization No. 8.5.

Example XV 396 grams of 85% potassium hydroxide and 820 grams of sulfonic acid concentrate in petroleum ether solution (36.6% stripping residue, having a neut. No. of 36.4), and 2700 grams of oil A were heated to distill the petroleum ether solvent and were blown with air at l./min. for three hours at 350 F. after which a filtered sample contained 3.5% potassium. After continued heating and air blowing for one hour to a temperature of 450 F. and for one hour at 450 F., the filtered product contained 5.2% potassium and 1.88% carbon dioxide.

The following example demonstrates the use of a synthetic base oil in the process of the invention:

Example XVI 458 grams of barium oxide were mixed with 2700 grams of butylene polymers and 54 ml. water and, while stirring, air was blown through the mixture at a rate of 10 l./min. while heating to 350 F. Then 300 grams of basic barium petroleum sulfonate (11% Ba) was added and the oxidation was continued three hours at 350 F. The temperature was then gradually raised over one hour to 450 F. and oxidation continued for one hour at 450 F. The filtered product contained 166% Ba by weight.

The physical tests characterizing the polybutylene polymer charged above include:

Flash, Cleveland Open Cup, F Viscosity, SSU at 100 F 111.5 Viscosity, SSU at 210 F 40.6 Molecular Weight 324 The following are examples of plant production of the metal complex-oil concentrate of the invention.

Example XVII The following ingredients were charged to a -barrel reaction kettle which was heated by automatically controlled electrical heating coils. The kettle was equipped with an 82.5 r.p.m. mixer having an impeller diameter of 34 inches. Battle plates were aiixed to the bottom of the kettle just outside the tips of the impeller blades. Air was caused to enter the kettle during the reacting period through two-one inch pipes with outlets diamctrically opposed about 3 inches above thc impeller blade tips. Spiral Water coils were installed in the kettle with necessary instrumentation to measure water iiow rate and record inlet and outlet temperature.

Ingredients: Amounts Refined parafin base distillate oil having an SUS viscosity at 210 F. of 54 and a pour of 10 F lbs 3710 Basic barium sulfonate -lbs 413 Barium oxide lbs 632 Water (distilled) lbs 74.3 Dimethyl silicone polymer conc gms-- 505 These ingredients were reacted in the kettle under the following reaction conditions:

Time at 350 F 5 hours.

Time at 350 F. to 450 F 1 hour.

Time at 450 F. w./air 1.3 hours.

Time at 450 F. w./N2 2.7 hours.

Air rate 0.232 l./l./min. (132 s.c.f.m.).

After completion of the reaction, the product had the following characteristics:

Barium content 8.9% (wt). Viscosity, at F., 1:1 kerosine blend 362 SSU CO2, percent 1.5 (approx.)

The approximate composition of the barium complexcontaining concentrate prepared as described above is as follows:

Barium carbonate percent (Wt.) 8.7 Ba(OH)2 do 2.3 Barium sulfonate do 4.4 Barium carboxylate do 7.3

Example XVIII The following ingredients were charged to the same type of reaction kettle as described in Example XV except that the diametrical opposed air inlet pipes were replaced by an air sparger.

Ingredients: Amount, lbs.

Refined paraffin base distillate oil having an SUS viscosity at 210 F. of 54 and a pour of Basic barium sulfonate 453.0 Barium oxide 694.0

Water 85.0 Dimethyl silicone polymer conc 1.2

These ingredients were reacted in the kettle under the following conditions:

After completion of the reaction the product was filtered and tested. The metal complex-concentrate had the following characteristics:

Barium content percent (wt.) 9.2 Kin. viscosity at 100 F cs 264.12 Viscosity index 106.8 Sulfur 0.48

Sulfated ash 16.48 CO2 percent 1.75 Neut. No. (alkaline) 0.25

In addition to the described batch processes of Examples XVII and XVIli. the invention contemplates means for producing tbe metal complex-concentrates disclosed which is useful either for a batch process or a continuous process. The producing means is shown in the accompanying drawing which is a schematic view of an oxidation reactor.

As seen in the drawing, oil and dispersant are charged to the kettle l through lines 2 and 4. The basic metal material, such as barium oxide is charged to the slurry tank 6 along with a small amount of oil to create the slurry, through lines 8 and 10. The base-oil slurry proceeds through line 2 to the kettle 1. Water is admitted to the kettle through line 12 while air is pumped through line 14 and is admitted to the reaction mixture through air sparger 16 or the like. Stirrer 18 continuously mixes the reaction mass during the reaction time. Kettle 1 is heated by conventional means such as automatically controlled electrical heating coils or the like. At the end of the oxidation period, nitrogen or other inert gas is admitted through line 20 while the flow of air through line 14 is stopped. When all the reaction conditions in accordance with the invention have been fulfilled the reaction mass is pumped through pump 22 into centrifuge 24. From centrifuge 24 the non-dispersed metal solids in the form of a slurry are thrown oft and returned to slurry tank 6 via line 26 while the crude product is passed through the filtering zone 28 from which the final product is received.

By-pass line 30 serves to avoid solids settling in the pump line which leads to the centrifuge or filter. Cooler 32 is required only in the event that the exothermic oxidation reaction evolves too much heat while heater 34 serves to maintain operating temperature when necessary.

Oxygenates collected in the condensate which is passed through the separation zone 36 are received at 38 while hydrocarbons are received at 40. These recovered materials constitute valuable by-products of the process.

The previously described reaction means for the process of this invention includes, for example, the use of two or more kettles, reactors or reaction zones so that an initial oxidation stage may be carried out in a first reaction zone at one temperature and then the reaction mass charged to another reaction zone for a second or overheat stage of oxidation. Another reaction zone can be provided as a holding zone in which the mass is blanketed with an inert gas while held at an elevated temperature. By employing two or more reaction zones the process of the invention is capable of continuous or semi-continuous operation since the reactants would then be charged continuously from one zone into the other in accordance with the reaction conditions of this invention.

Obviously, many modifications and variations of the invention as hereinabove set forth may be made without departing from the spirit and scope thereof, and therefore only such limitations should be made as are indicated in the appended claims.

We claim:

l. A process for preparing a detergent concentrate which comprises providing a reaction mixture consisting essentially of a major proportion of a hydrocarbon lubricating oil, about 1-35 percent by weight based on the weight of the mixture of a basic reacting metal compound selected from the group consisting of alkali metal and alkaline earth metal oxides, hydroxidcs and carbonates, and about 1-40 percent by weight based on the Weight of the mixture of a dispersant selected from the group consisting of' alkali metal and alkaline earth metal compounds of dispersant precursors of the class of oil soluble sulf'onic acids, alkyl (CMQ) phenols and sulfurized alkyl (CML.) phenols, and olefin polymer-phosphorus sulfide reaction products wherein the olefin polymer has a molecular weight in the range 40G-10,000, said reaction mixture having a total metal content providing a ratio of metal equivalents to equivalents of said dispersant precursor in the range from :1 to 100:1, respectively, heating the said mixture to about 350 F. and maintaining it at a temperature in about the range 350-550 F. for a total period of about 1-15 hours while blowing oxygen-containing gas therethrough at a rate of about 0.05l0.0 liters per minute per liter of the said mixture, said heating including a period from about 10 minutes to about 5 hours at a temperature in the range 40G-550 P., thereafter cooling the product obtained and removing any undissolved solid material to produce a clear and stable product containing 0.5-15 percent by weight of metal carbonate and 0.5-30 percent by weight of metal carboxylate.

2. The process according to claim l wherein said dispersant is a salt of petroleum sulfonic acids.

3. The process according to claim l wherein the said dispersant is an alkyl (CMQ) phenolate.

4. The process according to claim 1 wherein the said dispersant is a salt of an olefin-phosphorus sulfide reaction product wherein the olefin polymer has an average molecular weight in the range 500-1500.

5. The process according to claim 1 wherein the said reaction mixture contains about 1-30 percent of water.

6. The process according to claim 1 wherein the said oxygen containing gas is air, which is passed through the said reaction mixture at a rate of 0.1-3.0 liters of the said gas per liter of the said mixture per minute.

7. The process according to claim 1 wherein the said basic reacting metal compound is a barium compound.

8. The process according to claim 1 carried out so as to produce a iluid product wherein the metal content is about 6.9-14 times the initial amount of dissolved metal in the said reaction mixture.

9. The process according to claim 1 wherein the said mixture is maintained for at least 1 hour at a temperature in about the range 40G-550 F.

l0. The process according to claim 1 wherein the heating is carried out in two temperature stages the sec- 0nd of which is at least about 50 F. higher than the first.

11. The process according to claim 1 wherein the product obtained by said blowing with oxygen containing gas is heated in an inert atmosphere at a temperature in about the range 40C-550 F. for a period from about 15 minutes to about 3 hours.

l2. A process for preparing a detergent concentrate which comprises providing a reaction mixture consisting essentially of a major proportion of a hydrocarbon lubricating oil, about 5-35 percent by weight based on the weight of the mixture of a basic reacting metal compound selected from the group consisting of barium oxide, hydroxide and carbonate, about 1-40 percent by weight based on the weight of the mixture of barium petroleum sulfonate, and about 1-10 percent of water, said reaction mixture having a total metal content providing a ratio of metal equivalents to sulfonate equivalents in the range from 5:1 to 100:1, respectively, heating the said reaction mixture to about 350 F. and maintaining it at a temperature in about the range S50-550 for about 3-15 hours, at least about one hour of which is at a temperature of at least about 400 F., while blowing with air at a rate of about 0.1 to 3.0 liters per minute per liter of the said mixture, thereafter cooling the said product and removing any undissolved solid material to produce a clear and stable product containing 0.1-15 percent by weight of metal carbonate and 0.5-30 percent by weight of metal carboxylate.

13. The process according to claim 12 wherein the heating is carried out in two temperature stages the second of which is at least about 50 F. higher than the first.

14. The process according to claim 12 wherein the product obtained by said blowing with oxygen containing gas is heated in an inert atmosphere for about l5 minutes to three hours.

l5. The process according to claim 12 carried out so as to produce a fluid pro-duct containing about 3 5-16.6 percent by weight of barium.

16. The process according to claim l2 wherein the said hydrocarbon lubricating oil is a refined parafiinic mineral oil. l

17. The process according to claim 12 wherein the said hydrocarbon lubricating oil is an olcn polymer oil.

References Cited in the le of this patent UNITED STATES PATENTS 12 Vinograd et al. Mar. 9, 1954 Assef et al. Nov. 30, 19541-` Koft et al Jan. 29, 1957 Carlyle Nov. 25, 1958 Brooks July 2l, 1959 Carlyle May 24, 1960 Bartleson et al Oct. 4, 1960 

1. A PROCESS FOR PREPARING A DETERGENT CONCENTRATE WHICH COMPRISES PROVIDING A REACTION MIXTURE CONSISTING ESSENTIALLY OF A MAJOR PROPORTION OF A HYDROCARBON LUBRICATING OIL, ABOUT 1-35 PERCENT BY WEIGHT BASED ON THE WEIGHT OF THE MIXTURE OF A BASIC REACTING METAL COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL AND ALKALINE EARTH OXIDESM HYDROXIDES AND CARBONATES, AND ABOUT 1-40 PERCENT BY WEIGHT BASED ON THE WEIGHT OF THE MIXTURE OF A DISPERSANT SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL AND ALKALINE EARTH METAL COMPOUNDS OF DISPERSANT PRECURSORS OF THE CLASS OF OIL SOLUBLE SULFONIC ACIDS, ALKYL (C8-60) PHENOLS AND SULFURIZED ALKYL (C8-60) PHENOLS, AND OLEFIN POLYMER-PHOSPHORUS SULFIDE REACTION PRODUCTS WHEREIN THE OLEFIN POLYMER HAS A MOLECULAR WEIGHT IN THE RANGE 400-10,000, SAID REACTION MIXTUTE HAVING A TOTAL METAL CONTENT PROVIDING A RATIO OF METAL EQUIVALENTS TO EQIVALENTS OF SAID DISPERSANT PRECURSOR IN THE RANGE FROM 5:1 TO 100:1, RESPECTIVELY, HEATING THE MIXTURE TO ABOUT 350*F. AND MAINTAINING IT AT A TEMPERATURE IN ABOUT THE RANGE 350-550*F. FOR A TOTAL PERIOD OF ABOUT 1-15 HOURS WHILE BLOWING OXYGEN-CONTAINING GAS THERETHROUGH AT A RATE OF ABOUT 0.05-10.0 LITERS PER MINUTE PER LITER OF THE SAID MIXTURE, SAID HEATING INCLUDING A PERIOD FROM ABOUT 10 MINUTES TO ABOUT 5 HOURS AT A TEMPERATURE IN THE RANGE 400-550*F., THEREAFTER COOLING THE PRODUCT OBTAINED AND REMOVING ANY UNDISSOLVED SOLID MATERIAL TO PRODUCE A CLEAR AND STABLE PRODUCT CONTAINING 0.5-15 PERCENT BY WEIGHT OF METAL CARBONATE AND 0.5-30 PERCENT BY WEIGHT OF METAL CARBOXYLATE. 